Beijing National Laboratory for Molecular Sciences, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, People's Republic of China.
Inorg Chem. 2012 Feb 6;51(3):1590-8. doi: 10.1021/ic202295b. Epub 2012 Jan 11.
A dimetallic biscyclometalated ruthenium complex, (bpy)(2)Ru(dpb)Ru(bpy)(2) (bpy = 2,2'-bipyridine; dpb = 1,4-di-2-pyridylbenzene), with a tris-bidentate coordination mode has been prepared. The electronic properties of this complex were studied by electrochemical and spectroscopic analysis and DFT/TDDFT calculations on both rac and meso isomers. Complex (bpy)(2)Ru(dpb)Ru(bpy)(2) has a similar 1,4-benzenedicyclometalated ruthenium (Ru-phenyl-Ru) structural component with a previously reported bis-tridentate complex, (tpy)Ru(tpb)Ru(tpy) (tpy = 2,2';6',2″-terpyridine; tpb = 1,2,4,5-tetra-2-pyridylbenzene). The charge delocalizations of these complexes across the Ru-phenyl-Ru array were investigated and compared by studying the corresponding one-electron-oxidized species, generated by chemical oxidation or electrochemical electrolysis, with DFT/TDDFT calculations and spectroscopic and EPR analysis. These studies indicate that both (bpy)(2)Ru(dpb)Ru(bpy)(2) and (tpy)Ru(tpb)Ru(tpy) are fully delocalized systems. However, the coordination mode of the metal component plays an important role in influencing their electronic properties.
一种双金属双环金属化钌配合物，(bpy)(2)Ru(dpb)Ru(bpy)(2)（bpy=2,2'-联吡啶；dpb=1,4-二-2-吡啶基苯），具有三齿配位模式，已被制备。通过电化学和光谱分析以及 rac 和 meso 异构体的 DFT/TDDFT 计算研究了该配合物的电子性质。配合物(bpy)(2)Ru(dpb)Ru(bpy)(2)具有与先前报道的双三齿配合物(tpy)Ru(tpb)Ru(tpy)（tpy=2,2';6',2″-三联吡啶；tpb=1,2,4,5-四-2-吡啶基苯）相似的 1,4-苯二环金属化钌（Ru-苯基-Ru）结构部分。通过研究通过化学氧化或电化学电解产生的相应单电子氧化物种，用 DFT/TDDFT 计算、光谱和 EPR 分析研究了这些配合物在 Ru-苯基-Ru 阵列上的电荷离域，并进行了比较。这些研究表明，(bpy)(2)Ru(dpb)Ru(bpy)(2)和(tpy)Ru(tpb)Ru(tpy)都是完全离域的体系。然而，金属部分的配位模式在影响它们的电子性质方面起着重要作用。
